Water-insoluble monoazo dyes containing a 2,1-benzoisothiazolyn-(3) radical



United States Patent Int. Cl. coab 29/36 Us. (:1; 260-158 7 Claims ABSTRACT OF THE DISCLOSURE Disperse monoazo dyes of a 3-amino-benzisothiazole as the diazo component and N-substituted aniline as the coupling component, said dyes being useful for application to textile materials of cellulose acetate, polyesters and polyamides.

This invention relates to new water-insoluble monoazo dyes containing a 2,1-benzoisothiazolyl-(3) radical.

The new compounds are disperse dyes suitable for dyeing materials made of cellulose acetate, synthetic linear polyesters and polyamides.

In particular this invention relates to monoazo dyes of the general formula:

in which X and Y denote hydrogen, chlorine or bromine atoms of nitro, trifluoromethyl, alkoxy, carbalkoxy, acylamino or alkylsulfone groups, the last four each having one to four carbon atoms, A denotes a substituted or unsubstituted para-phenylene radical, R denotes a hydrogen atom or a substituted or unsubstituted alkyl radical having one to four carbon atoms, and R denotes a substituted or unsubstituted alkyl radical.

Specific examples of radicals X and Y are: hydrogen, nitro, chloro, bromo, methyl, ethyl, methoxy, ethoxy, carbomethoxy, carboethoxy, trifluoromethyl, metbylsulfonyl, ethylsulfonyl, acetylamino or propionylamino.

Especially interesting and valuable compounds are those having the general formula.

in which X denotes a hydrogen, chlorine or bromine atom or a nitro, alkoxy or alkylsulfone group, Y denotes a hydrogen, chlorine or bromine atom or a nitro, alkoxy or alkylsulfone group, R denotes a hydrogen atom or an alkyl or alkoxy group each having one to four carbon atoms, R denotes a hydrogen, chlorine or bromine atom or an alkyl, alkoxy or acylamino group each having one to four carbon atoms or a trifluoromethyl group, R denotes a hydrogen atom or an alkyl, cholroalkyl, bromoalkyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl 3,455,898 Patented July 15, 1969 ICE or carbalkoxyalkyl group, all alkyl, alkoxy, acyl or carbalkoxy groups having one to four carbon atoms, and R denotes an alkyl, chloroalkyl, bromoalkyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl or carbalkoxyalkyl group, all alkyl, alkoxy, acyl or carbalkoxy groups having one to four carbon atoms.

The following radicals may be given as specific examples of R and R methyl, ethyl, propyl, butyl, B-cyanoethyl, fi-hydroxyethyl, 18,'y-dihydroxypropyl, fi-hydroxy-vchloropropyl, carbomethoxyethyl, carboethoxyethyl, carbomethoxypropyl, acetoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, methoxyethly, ,B-chloroethyl and butane-3-one-1-yl.

Coupling components for the production of the new dyes are for example:

N-ethylaminob enzene, Nbutylaminobenzene, N-cyanoethylarninob enzene, N-methoxyethyl-3-methylbenzene, N-cyano ethyl-3 -chlorobenzene, N,N-diethylarninob enzene, N-ethyl-N-fi-hydroxyethylaminobenzene, N-ethyl-N-fl-cyanoethylaminobenzene, N-B-hydroxyethyl-N-B-cyanoethylaminobenzene, N-ethylN-fi-acetoxyethylaminob enzene, N-ethyl-N-B-methoxyethylaminob enzene, N-B-acetoxyethyl-N-fi-cyanoethylaminobenzene, N,N-di- B-hydroxyethyl) -aminobenzene, N-fl-carb omethoxyethyl-N-fi-hydroxyethylarninobenzene, N-fi-acetoxyethyl-N-fi-hydroxyethylaminobenzene, N-p-metho xyethyl-N-B-hydroxyethylamin obenzene, N-B-methoxyethyl-N-fl-cyanoethylaminobenzene, N-B-methoxyethyl-N-fi-carbomethoxyethylaminobenzene, N-B-methoxyethyl-N-B-acetoxyethylaminobenzene, N-B-methoxyethyl-N- (butane-3 -0ne- 1-yl)-aminobenzene, N-ethyl-N-fl-cyanoethyl-F; -methylaminob enzene, N-ethyl-N-fi-hydroxyethyl-S -methylaminobenzene, N-ethyl-N-v-acetylaminopropyl-3 -methylaminobenzene, N,N-di- ,B-hydroxyethyl) -3-methylarninobenzene, N-fl-cyanoethyl-N-p-hydroxyethyl-3-methylaminob enzene, N- S-cyanoethyl-N-[S-methoxyethyl-3-rnethylaminobenzene, N-fi-cyanoethyl-N-butyl-B -methylaminobenzene, N-fi-hydroxyethyl-N-b utyl-3 -methylaminob enzene, N-B-chloroethyl-N-butyl-3 -methylarninobenzene, N- S-chloroethyl-N-fi-methoxyethyl-Zi-methylaminobenzene, N,N-di- (pi-hydroxyethyl) -3-chl0roaminobenzene, N-B-hydroxyethyl-N-B-cyanoethyl-3-chloroaminobenzene, N,N-di- B-hydroxyethyl) -3 -acetylaminoaminobenzene, N-[i-hydroxyethy1-N-B-cyanoethyl-3-acetylaminoaminobenzene, N,N-difl-hydroxyethyl) -2-methoxy-5-acetylaminoaminobenzene, and N-B-hydroxyethyl-N-fi-cyanoethyl-Z-methoxy-S-acetylaminoaminob enzene.

The diazo components for the production of the new dyes are obtainable by methods described in the literature. They are obtained particularly simply by reaction of ortho-aminobenzonitriles with hydrogen sulfide followed by oxidation for example by the method described in Belgian patent specification No. 670,652.

The dyes obtainable according to the invention are eminently suitable, particularly in finely divided form, for dyeing materials such as fibers, filaments, threads, flock, woven fabrics and knitted fabrics of cellulose acetate (secondary acetate and triacetate), linear polyesters and polyamides.

The dyeings obtained are distinguished by good fastness and' good alfinity. Wet fastness and fastness to light, gas fume fading and heat, which in many cases are excellent, should be particularly emphasized.

The parts and percentages specified in the following examples, which will further illustrate the invention, are by Weight; parts by volume bear the same relation to parts by weight as the liter (STP) to the kilogram.

Example 1 3.75 parts of 3-amino-2,l-benzoisothiazole is dissolved at 25 C. in 14 parts of concentrated sulfuric acid. Then at to C., first 3 parts of a mixture of glacial acetic acid and propionic acid (17:3) is allowed to drip in and diazotization is carried out at this temperature by gradual addition of 7.25 parts of uitrosylsulfuric acid (having a content of 13.1% of free dinitrogen trioxide). The whole is stirred for one hour and then 0.4 part of urea is added.

The clear diazo solution thus obtained is allowed to flow gradually into a solution consisting of 4.2 parts of N-B-hydroxyethyl-N-ethyl-aminobenzene, 300 parts of water, 3 parts of concentrated hydrochloric acid, parts of sodium acetate, and parts of ice. The dye, precipitated in crystalline form, is stirred for one hour, suction filtered, washed with water until neutral and dried at 50 C. at subatmospheric pressure.

The dye thus obtained dyes cellulose acetate ruby red shades having very good fastness to light. The dye goes on to polyethylene glycol terephthalate and polyamide in full ruby red shades.

If the components set out in the following table be used instead of the coupling component specified in Example 1, dyes having the same good properties are obtained.

Shade of dyeing on- Example No. Coupling component Acetate Polyamide Polyester CzH5 2 N\ Ruby Red brown Red.

C2115 3 N\ ..do Claret Ruby.

C EH40 ICE-CH3 O C2H4OH 4 N\ do Red violet Do.

CiH4OH /CH4OH 5 N\ Red Red brown Red.

CgHgCN CQHAOH t: N\ Red Brown red Red.

C 2H4C O 3 CH3 C 2H4OH 4 N\ Ruby Claret Ruby.

C zHgO CH3 C H40H s N\ .do do Do.

C1H40 C-CH: I]

C H CN 9 N\ do Red brown Red.

CQH4O CH3 2H4CN 1O N\ .-..do do Red.

611140 C-CHa ll /C=H4O CH8 11 N\ Red Brown red Red.

CgHiC O: CH; /C:H4O CH! 12 N\ Red do Red.

C2H4O fiJ-C Ha 0 /C:H4O CH; 13 N Ruby Red brown Red.

Shade 0! dyeing on Example N o. Coupling component Acetate Polyamide Polyester /C;H5 14 @N\ Blue red Red violet Blue red.

I C2H4CN CH:

/CgH5 15 N\ Violet Violet Violet.

I C HNHG O CH; CH3

/C:H4OH 16 l- N\ Ruby Red brown. Ruby.

1 C2H4GN CH:

/CzH OH 17 N\ Violet Blue violet Violet.

| C2H4O H CH3 /C;|H5 18 N\ Blue violet ..do Blue violet.

I sumo H CH3 /OH4CN 19 N\ Ruby Red brown Ruby.

I C2H4O GHa CH3 /C3H4CN 2O N\ Blue red Red violet; Blue red.

C4119 21 N\ ..do .do Do.

A} C2H4Cl /C: 4Cl 22 N\ Ruby Red brown. Ruby.-

| CzH4O CH; CH:

/C H4O H 23 N\ Red violet Red violet Do.

/C1H4OH 24. N\ Blue red Red brown Red brown.

I C2H4ON Cl /C2H4OH 25.. N\ Violet Violet blue Violet.

| aEON HN-C 0 CH3 /C H4OH 26 N\ Red violet Currant Do.

| CzHlON HN-C 0 CH1:

d'-/C H4OH 27 N\ Navy blue.. Blue Blue:

] CIHIOH HN-C O CH:

O OH:

/C:H4OH 28 N\ Blue violet Violet blue Navy blue.-

CZHACN HIV-CO CH3 7 Example 29 4.88 parts of 3-amino-5-nitro-2,l-benzoisothiazole is dissolved at 10 to C. in 60 parts of concentrated sulfuric acid. Into this solution at 0 to 5 C., first parts of a mixture of glacial acetic acid and propionic acid (17:3) and then 7.45 parts of nitrosylsulfuric acid (having a content of 12.8% of free dinitrogen trioxide) is dripped. The resultant clear diazo solution is stirred for three hours at 0 to 5 C. and then allowed to flow into a solution of 4.9 parts of N,N-di-(fi-hydroxyethyl)-3-methylaminobenzene, 500 parts of water, 3 parts of concentrated hydro- Shade of dyeing on- Example N 0. Coupling component Acetate Polyamide Polyester 02115 N Violet Gray blue Violet.

CzH4ON O2H4OH 31 N Blue violet Blue violet Blue violet.

CeHlO CH3 I CgHlCN 32 N Turquoise Green Blue green.

] C2H4O H HN-O 0 CH3 C2H4OH 33 N Green blue do Green.

I CZH4OH HN-C 0 CH3 0:135 34 N Blue Blue Blue.

CzH4OH CgHgCN 35 @4/ Red blue d0 D0.

\C:HH

C H4OH as QN Blue Blue violet Navy blue.

(IJ1 C:H40H

031E CH3 3? Q-N do Blue Blue.

\CQHQC 0 CH O2H4O CH: 38 @4/ Violet Violet Violet.

C2H4CN CgHg 39 N 0 Green blue Turquoise Turquoise.

CH3 C HeNH JCH CgHrO CH3 40 N Blue Blue Blue.

oeHlo C-CH;

C5|H4OH 41 QN Red blue .do Do.

CzH4C OQCHB CH3 42 N Blue .do Do.

Example 43 By using 7.7 parts of Z-arn'mo-Z,l-benzoisothiazole and 4.9 parts of N,N-di-(,8-hydroxyethyl)-3-methylaminobenzene (instead of the 3.75 parts of 3-amino-2,1-benzoisothiazole and 4.2 parts of N-fi-hydroxyethyl-N-ethylaminobenzene specified in Example 1) and following the procedure of the first paragraph of Example 1, a dye is obtained which dyes polyamide bright blue shades having very good fastness to washing, perspiration and heat setting.

Dyes having similar properties are obtained by using the coupling components specified in the above tables instead of N,N-di-(B-hydroxyethyl)-3-methylaminobenzene.

We claim:

1. A disperse monoazo dye of the formula:

wherein:

X and Y each denote a substituent selected from the class consisting of hydrogen, chlorine, bromine, nitro, trifluoromethyl, alkoxy of 1 to 4 carbon atoms, carbalkoxy of 1 to 4 carbon atoms, alkanoylamino of 1 to 4 carbon atoms and alkylsulfone of 1 to 4 carbon atoms;

R denotes a substituent selected from the class consisting of hydrogen, alkyl of 1 to 4 carbon atoms and alkoxy of 1 to 4 carbon atoms;

R denotes a substituent selected from the class consisting of hydrogen, bromine, chlorine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and alkanoylamino of 1 to 4 carbon atoms;

R denotes a substituent selected from the class consisting of hydrogen, alkyl, chloroalkyl, bromoalkyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkanoyloxyalkyl and carbalkoxyalkyl, each of the alkyl, alkoxy, alkanoyl and carbalkoxy radicals having 1 to 4 carbon atoms; and

R denotes a substituent selected from the class consisting of alkyl, chloroalkyl, bromoalkyl, cyanoalkyl, hydroxyalkyl, alkoxyalkyl, alkanoyloxyalkyl and carbalkoxyalkyl, each of the alkyl, alkoxy, alkanoyl and carbalkoxy radicals having 1 to 4 carbon atoms.

2. A disperse monoazo dye of the formula:

wherein:

X denotes a substituent selected from the class consisting of hydrogen, chlorine and bromine;

Y denotes a substituent selected from the class consisting of hydrogen and nitro;

R denotes a substituent selected from the class consisting of hydrogen, alkyl of 1 to 4 carbon atoms and alkoxy of 1 to 4 carbon atoms;

R denotes a substituent selected from the class consisting of hydrogen, bromine, chlorine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and alkanoylamino of 1 to 4 carbon atoms;

R denotes a substituent selected from the class consisting of hydrogen, alkyl, chloroalkyl, bromoalkyl,

S OzN V l C H2 C 112-0 E NHCO CH3 4. The compound having the formula:

CQH C o 0 CH;

5. The compound having the formula:

6. The compound having the formula:

CHz-CHr-OH 7. The compound having the formula:

CHz-GHPOH N References Cited UNITED STATES PATENTS 2/1939 Heinrich et al. 260-158,XR 5/1944 Back 260-158 XR 4/ 1945 McNally et al. 260-158 XR 3/1957 Straley et al 260-158 6/1959 Bossard et a1. 260-158 XR 6/1959 Merian 260-158 XR 10/1962 Dehn et al. 260-158 FLOYD D. HIGEL, Primary Examiner U.S. Cl. X.R. 8-41, 50; 260-304, 465, 471, 490, 562, 573, 574 

